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Title: Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment

Abstract

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin-type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries - Re[BCP]O and Re[BCP]O2. To our surprise, single-crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re-C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans-ReVII(O)2 center. The search for metal valence states >6 in porphyrin-type ligand environments must therefore continue.

Authors:
 [1];  [2];  [3];  [1]
  1. Department of ChemistryUiT – The Arctic University of Norway 9037 Tromsø Norway
  2. Centro de Química, Instituto de CienciasUniversidad Autónoma de Puebla Edif. IC9, CU, San Manuel 72570 Puebla, Puebla Mexico
  3. Advanced Light SourceLawrence Berkeley National Laboratory Berkeley CA 94720–8229 USA
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Research Council of Norway
OSTI Identifier:
1570860
Alternate Identifier(s):
OSTI ID: 1570861; OSTI ID: 1580950
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
ChemistryOpen
Additional Journal Information:
Journal Name: ChemistryOpen Journal Volume: 8 Journal Issue: 10; Journal ID: ISSN 2191-1363
Publisher:
ChemPubSoc Europe
Country of Publication:
Germany
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Alemayehu, Abraham B., Vazquez‐Lima, Hugo, Teat, Simon J., and Ghosh, Abhik. Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment. Germany: N. p., 2019. Web. doi:10.1002/open.201900271.
Alemayehu, Abraham B., Vazquez‐Lima, Hugo, Teat, Simon J., & Ghosh, Abhik. Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment. Germany. doi:10.1002/open.201900271.
Alemayehu, Abraham B., Vazquez‐Lima, Hugo, Teat, Simon J., and Ghosh, Abhik. Fri . "Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment". Germany. doi:10.1002/open.201900271.
@article{osti_1570860,
title = {Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment},
author = {Alemayehu, Abraham B. and Vazquez‐Lima, Hugo and Teat, Simon J. and Ghosh, Abhik},
abstractNote = {A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin-type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries - Re[BCP]O and Re[BCP]O2. To our surprise, single-crystal structure determination of one of the complexes of the latter type indicated an ReVO center with a second oxygen bridging the Re-C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans-ReVII(O)2 center. The search for metal valence states >6 in porphyrin-type ligand environments must therefore continue.},
doi = {10.1002/open.201900271},
journal = {ChemistryOpen},
number = 10,
volume = 8,
place = {Germany},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1002/open.201900271

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